Science of Synthesis. Houben Weyl Methods of Molecular Transformations. P. J. Reider E. Schaumann I. Shinkai E. J. Thomas B. M.

Transcription

1

2 Science of Synthesis Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis. Science of Synthesis presents the important synthetic methods for all classes of compounds and includes: Methods critically evaluated by leading scientists Background information and detailed experimental procedures Schemes and tables which illustrate the reaction scope

3 Science of Synthesis Houben Weyl Methods of Molecular Transformations Editorial Board D. Bellus E. N. Jacobsen S. V. Ley R. Noyori M. Regitz P. J. Reider E. Schaumann I. Shinkai E. J. Thomas B. M. Trost Managing Director G. F. Herrmann Managing Editor Senior Scientific Editor M. F. Shortt de Hernandez M. H. Smith Scientific Editors K. E. du Plooy L. A. Telan I. M. Thomas M. J. White Assistant Scientific Editor A. G. Russell b Georg Thieme Verlag KG Stuttgart New York

4 Science of Synthesis Houben Weyl Methods of Molecular Transformations Category 6 Volume 44 Volume Editor Compounds with All-Carbon Functions Cumulenes and Allenes N. Krause Responsible Member of the Editorial Board D. Bellus Authors V. Gandon A. S. K. Hashmi T. Kawase M. Malacria M. Ogasawara H. Ohno H.-U. Reissig M. A. Tius K. Tomioka K. K. Wang R. Zimmer b 2008 Georg Thieme Verlag KG Stuttgart New York

5 IV 2008 Georg Thieme Verlag KG Rüdigerstrasse 14 D Stuttgart Printed in Germany Typesetting: Ziegler + Müller, Kirchentellinsfurt Printing: Gulde Druck, Tübingen Binding: J. Spinner, Ottersweier Bibliographic Information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available on the internet at < Library of Congress Cataloging in Publication Data Science of synthesis : Houben Weyl methods of molecular transformations. p. cm. Includes bibliographical references and index. Contents: category 6. Compounds with All-Carbon Functions. v. 44. Cumulenes and Allenes / volume editor, N. Krause ISBN ISBN (v. 44) 1. Organic compounds Synthesis. I. Title: Houben Weyl methods of molecular transformations. QD262.S '.2 dc (Houben Weyl methods of organic chemistry) British Library Cataloguing in Publication Data Science of Synthesis : Houben Weyl methods of molecular transformations. Category 6: Compounds with All-Carbon Functions: Vol. 44: Cumulenes and Allenes. (Houben Weyl methods of organic chemistry) 1. Organic compounds Synthesis 2. Organic compounds Synthesis Laboratory manuals I. Krause, N., II. Gandon, V ISBN (Georg Thieme Verlag KG, Stuttgart) ISBN (Thieme New York) Date of publication: December 12, 2007 Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as well as of translation. No part of this publication may be reproduced by any process, whether by photostat or microfilm or any other procedure, without previous written consent by the publisher. This also includes the use of electronic media of data processing or reproduction of any kind. This reference work mentions numerous commercial and proprietary trade names, registered trademarks and the like (not necessarily marked as such), patents, production and manufacturing procedures, registered designs, and designations. The editors and publishers wish to point out very clearly that the present legal situation in respect of these names or designations or trademarks must be carefully examined before making any commercial use of the same. Industrially produced apparatus and equipment are included to a necessarily restricted extent only and any exclusion of products not mentioned in this reference work does not imply that any such selection of exclusion has been based on quality criteria or quality considerations. Warning! Read carefully the following: Although this reference work has been written by experts, the user must be advised that the handling of chemicals, microorganisms, and chemical apparatus carries potentially life-threatening risks. For example, serious dangers could occur through quantities being incorrectly given. The authors took the utmost care that the quantities and experimental details described herein reflected the current state of the art of science when the work was published. However, the authors, editors, and publishers take no responsibility as to the correctness of the content. Further, scientific knowledge is constantly changing. As new information becomes available, the user must consult it. Although the authors, publishers, and editors took great care in publishing this work, it is possible that typographical errors exist, including errors in the formulas given herein. Therefore, it is imperative that and the responsibility of every user to carefully check whether quantities, experimental details, or other information given herein are correct based on the users own understanding as a scientist. Scaleup of experimental procedures published in Science of Synthesis carries additional risks. In cases of doubt, the user is strongly advised to seek the opinion of an expert in the field, the publishers, the editors, or the authors. When using the information described herein, the user is ultimately responsible for his or her own actions, as well as the actions of subordinates and assistants, and the consequences arising therefrom.

6 V Preface As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben Weyl Methods of Organic Chemistry will be published starting in the year To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century. Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described. The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century. We would like to thank all of our authors for submitting contributions of such outstanding quality, and, also for the dedication and commitment they have shown throughout the entire editorial process. The Editorial Board October 2000 D. Bellus (Basel, Switzerland) P. J. Reider (New Jersey, USA) E. N. Jacobsen (Cambridge, USA) E. Schaumann (Clausthal-Zellerfeld, Germany) S. V. Ley (Cambridge, UK) I. Shinkai (Tsukuba, Japan) R. Noyori (Nagoya, Japan) E. J. Thomas (Manchester, UK) M. Regitz (Kaiserslautern, Germany) B. M. Trost (Stanford, USA)

7

8 VII Volume Editors Preface Whereas allenes and higher cumulenes have been regarded as chemical curiosities for a long time, they are now recognized not only as valuable synthetic precursors for complex molecules of biological or industrial interest, but also as intriguing target molecules in their own right. Thus, it is not surprising that a surge of new synthetic methods for allenes and cumulenes has taken place in recent years. Volume 44 of Science of Synthesis provides a well-organized overview of all these methods, together with a section on the applications of allenes in organic synthesis. I am very grateful to the authors for their outstanding commitment to this venture. It was a pleasure to plan the volume with the exceptional experience and insight provided by Dr. Daniel Bellus and Dr. Joe Richmond, and to bring it into existence with the immense support of the Thieme editorial team headed by Dr. Fiona Shortt de Hernandez. In particular, I thank Dr. Caroline J. Taylor, Dr. Marcus White, and Dr. Mark Smith for their great help throughout editing of the chapters. Special mention goes to Angela Gilden and Michaela Frey for their smooth handling of the (quite substantial) paperwork. Volume Editor Norbert Krause Dortmund, November 2007

9

10 IX Volume 44: Cumulenes and Allenes Preface... V Volume Editors Preface... VII Table of Contents... XI Introduction N. Krause Product Class 1: Cumulenes M. Ogasawara Product Class 2: Linear Allenes Synthesis by Substitution H. Ohno and K. Tomioka Synthesis by Elimination V. Gandon and M. Malacria Synthesis by Addition K. K. Wang Synthesis by Rearrangement A. S. K. Hashmi Synthesis from Other Allenes H.-U. Reissig and R. Zimmer Applications of Allenes in Organic Synthesis M. A. Tius Product Class 3: Cyclic Allenes T. Kawase Keyword Index Author Index Abbreviations

11

12 XI Table of Contents Introduction N. Krause Introduction Product Class 1: Cumulenes M. Ogasawara 44.1 Product Class 1: Cumulenes Product Subclass 1: [6]- and Higher Cumulenes Synthesis of Product Subclass Synthesis by Elimination Method 1: Reduction of Æ,w-Dihydroxypolyynes Method 2: Double Elimination of Methanol from 1,7-Dimethoxyhepta-2,4-diynes Product Subclass 2: Hexapentaenes ([5]Cumulenes) Synthesis of Product Subclass Synthesis by Elimination Method 1: Dehydroxylation of Hexa-2,4-diyne-1,6-diols Method 2: Debromination of 3,4-Dibromohexa-1,2,4,5-tetraenes Method 3: Other Methods Involving Elimination Synthesis Mediated by Carbene Species Method 1: Dimerization of Allenylidene Species Variation 1: Dimerization of Allenylidene Species Generated from Propargylic Precursors Variation 2: Dimerization of Allenylidene Species Generated from Bromoallenes Variation 3: Dimerization of Allenylidene Chromium Species Method 2: Trapping of Hexapentaenylidene Species Product Subclass 3: Pentatetraenes ([4]Cumulenes) Synthesis of Product Subclass Synthesis by Substitution Method 1: Lithiation and Silylation of Hexa-2,4-diynes Method 2: S N 2 Substitution on Penta-2,4-diynyl Esters Synthesis by Elimination Method 1: Double Dehydrobromination of 2,4-Dibromopenta-1,4-dienes Method 2: 1,2- and 1,4-Elimination from 5-Methoxypent-2-yn-1-ols... 20

13 XII Table of Contents Method 3: Oxidation of Hexapentaenes Followed by Carbon Monoxide Elimination Method 4: Reductive 1,4-Dechlorination of a 2,5-Dichloropent-1-en-3-yne Method 5: 1,1-Dehalogenation and Rearrangement of 1,1-Dihalocyclopropanes Method 6: Sulfur Elimination from Penta-1,2,3,4-tetraene Episulfides Method 7: Wittig Reaction Variation 1: Wittig Reaction of Carbon Suboxide with Alkylidenephosphoranes Variation 2: Wittig Reaction of Alka-2,3-dienoyl Chlorides with Alkylidenephosphoranes Method 8: Retro-Diels Alder Reaction Product Subclass 4: Butatrienes ([3]Cumulenes) Synthesis of Product Subclass Synthesis by Substitution Method 1: S N 2 Substitution on Pent-4-en-2-ynyl Derivatives and Related Reactions Variation 1: On Pent-4-en-2-ynyl Methanesulfinates with Alkylsilver(I) Reagents Variation 2: On 2-(But-3-en-1-ynyl)oxiranes with Alkylsilver(I) Reagents Variation 3: Reduction of Alka-4,5-dien-2-ynols or Related Alcohols by Lithium Aluminum Hydride Method 2: S N 2 Substitution on 2-Bromo-1-en-3-ynes Variation 1: With Alkylcopper Reagents Variation 2: With Soft Carbon Nucleophiles Catalyzed by a Palladium Complex Method 3: Synthesis of Phosphinobutatrienes from 2-Vinyl-1H-phosphirenes and Alkyllithium Reagents Synthesis by Elimination Method 1: Dehydrohalogenation Variation 1: Single Dehydrohalogenation of Haloallenes Variation 2: Double Dehydrohalogenation of 2,3-Dihalobut-2-enes Variation 3: Double Dehydrohalogenation of 1,4-Dihalobut-2-enes Variation 4: Double Dehydrochlorination and Ring Opening of 1,1-Dichlorocyclopropanes Method 2: Dehydration Variation 1: 1,2-Dehydration of Alka-2,3-dienols Variation 2: Rearrangement and Dehydration of Epoxyalkynols Method 3: Elimination of Alcohols and Related Reactions Variation 1: 1,4-Elimination of Alcohols Variation 2: 1,6-Elimination of Alcohols Method 4: Pyrolysis of Hexakis(trimethylsilyl)but-2-yne Method 5: Dehalogenation Variation 1: 1,4-Dehalogenation of 1,4-Dihaloalk-2-ynes Variation 2: 1,2-Dehalogenation of 2,3-Dihalo-1,3-dienes... 39

14 Table of Contents XIII Method 6: 1,1-Dehalogenation and Rearrangement of 2-Alkenylidene-1,1-dihalocyclopropanes Method 7: Dehydroxylation of Alk-2-yne-1,4-diols Method 8: 1,4-Elimination from 4-Hydroxybut-2-ynylsilanes or -stannanes Variation 1: From 4-Hydroxybut-2-ynylsilanes Variation 2: From 4-Hydroxybut-2-ynylstannanes Method 9: Desulfurization of Cyclic Trithiocarbonates Method 10: Sulfur Elimination from Alkylidenecyclopropanethiones Method 11: Wittig and Related Reactions Variation 1: Wittig Reaction of Aldehydes or Ketones with Allenylidenephosphoranes Variation 2: Double Wittig Reaction of a Phosphorus Diylide with an Aldehyde Variation 3: Horner Emmons-Type Reactions of Aldehydes or Ketones Variation 4: Wittig Reaction of a Ketene with a Vinylidenephosphorane Method 12: Base-Induced Borane Elimination from Bis(1-iodoalkenyl)boranes Method 13: Retro-Diels Alder Reactions Method 14: Thermal Decomposition of a Disodium Salt of a Cyclobutane-1,3-dione Bis(tosylhydrazone) Synthesis by Addition Method 1: Electrophilic 1,4-Addition to 1,3-Diynes Method 2: 1,4-Disilylation of 1,4-Disilyl-1,3-diynes Variation 1: 1,4-Disilylation of 1,4-Disilyl-1,3-diynes by a Silylmanganese Reagent Variation 2: Palladium-Catalyzed 1,4-Disilylation of 1,4-Disilyl-1,3-diynes Method 3: Palladium-Catalyzed Double Arylation of 1,4-Diaryl-1,3-diynes Method 4: 1,6-Addition of Bromine to 1,5-Dien-3-ynes Synthesis by Rearrangement Method 1: Base-Promoted Rearrangement of a Conjugated Bisallene to an Alkenylbutatriene Method 2: Photorearrangement of Vinylidenecyclopropanes to Butatriene Derivatives Synthesis Mediated by Carbene Species Method 1: Dimerization of Vinylidene Species or Vinylidene Equivalents Variation 1: Dimerization of Vinylidene Species or Vinylidene Equivalents Generated from gem-dihaloalkenes Variation 2: Dimerization of Vinylidene Species or Vinylidene Equivalents Generated from 1-Halo-1-hydroalkenes Variation 3: Formation of a Butatriene from 2-Nitro-1,1-diphenylethene Variation 4: Dimerization of Alkenylidene Species Generated from Dialkenylcuprates Variation 5: Desulfurization Dimerization of Dithioacetals with Hexacarbonyltungsten(0) Variation 6: Dimerization of Vinylidene Tungsten Species Method 2: Reactions Involving Allenylidene Species... 60

15 XIV Table of Contents Variation 1: Reactions of Allenylidene Species with Diazoalkanes Variation 2: Reactions of Allenylidene Rhodium Complexes with Diazomethane Method 3: Reactions of 1,2,3-Trienylidene Species Variation 1: Reactions of 1,2,3-Trienylidene Species with Alkenes Variation 2: Reactions of 1,2,3-Trienylidene Species with Group 14 Hydrides Other Methods for the Synthesis of Butatrienes Method 1: Dimerization of Terminal Alkynes by Transition-Metal Catalysts Method 2: Coupling Reactions between 1,1-Dichloroalkenes and Terminal Alkenes Method 3: Zirconium-Mediated Coupling Reactions of 1,3-Diynes with Aldehydes or Ketones Variation 1: Reactions of Zirconacycles with Aldehydes To Form Butatrienyl Monoalcohols Variation 2: Reactions of Zirconacycles with Ketones To Form Butatrienyl Diols Product Class 2: Linear Allenes Synthesis by Substitution H. Ohno and K. Tomioka Synthesis by Substitution Method 1: Organocopper-Mediated Reactions of Propargylic and Related Substrates Variation 1: Reactions of Various Propargylic Substrates Variation 2: Reactions Using Various Copper Nucleophiles Variation 3: Synthesis of Enantiomerically Enriched Allenes Variation 4: Ring-Opening Reactions Variation 5: 1,5-Substitution Reactions Variation 6: Halogenation of Propargylic Substrates Method 2: Aluminum-Mediated Reactions of Propargylic Substrates Variation 1: Reactions of Propargylic Halides Variation 2: Reactions of Propargylic Alcohols Variation 3: Reactions of Propargylic Sulfonates Variation 4: Reactions of Propargylic Ethers Variation 5: Reactions of Propargylic Amine Derivatives Variation 6: Ring-Opening Reactions Variations 7: Miscellaneous Reactions Method 3: Lithium-, Magnesium-, or Zinc-Mediated Reactions of Propargylic and Related Substrates Variation 1: Lithium-Mediated Reactions Variation 2: Magnesium-Mediated Reactions Variation 3: Zinc-Mediated Reactions